JP2001149780A - Method for manufacturing ammonia and ammonia synthesizing gas - Google Patents
Method for manufacturing ammonia and ammonia synthesizing gasInfo
- Publication number
- JP2001149780A JP2001149780A JP2000328905A JP2000328905A JP2001149780A JP 2001149780 A JP2001149780 A JP 2001149780A JP 2000328905 A JP2000328905 A JP 2000328905A JP 2000328905 A JP2000328905 A JP 2000328905A JP 2001149780 A JP2001149780 A JP 2001149780A
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- catalyst
- ruthenium
- carrier
- nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract 3
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- 229910052582 BN Inorganic materials 0.000 claims abstract description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011149 active material Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000012876 carrier material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- -1 carbon Chemical compound 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、金属窒化物キャリ
ア上に支持された触媒活性材料としてのルテニウムを含
むアンモニア合成触媒とアンモニア合成ガスとを接触さ
せることによってアンモニアを合成する方法に関する。TECHNICAL FIELD The present invention relates to a method for synthesizing ammonia by contacting an ammonia synthesis gas containing ruthenium as a catalytically active material supported on a metal nitride carrier with an ammonia synthesis gas.
【０００２】[0002]
【従来の技術】アンモニア合成ガスからのアンモニアの
合成に使用されるルテニウムに基づく触媒は当業界にお
いて公知である（米国特許第4,600,571 号、特開平9-16
8739号及びイギリス特許出願公開第2,033,766 号）。BACKGROUND OF THE INVENTION Ruthenium-based catalysts used for the synthesis of ammonia from ammonia synthesis gas are known in the art (US Pat. No. 4,600,571;
8739 and United Kingdom Patent Application Publication No. 2,033,766).
【０００３】高価なルテニウムの必要量をできるだけ低
く抑えるために、このような触媒は、通常、活性ルテニ
ウム粒子の利用可能な表面積を最大限に高める目的でキ
ャリア材料により支持する。[0003] In order to keep the required amount of expensive ruthenium as low as possible, such catalysts are usually supported by a carrier material in order to maximize the available surface area of the active ruthenium particles.
【０００４】接触的アンモニア合成に適当なものとして
幾つかの支持体が提案されている。このような材料には
MgO 、Al2O3 及びMgAl2O4 などがある。現在では、最も
活性の高いルテニウム触媒は、キャリア材料としての黒
鉛化した炭素上に支持されたものである。Several supports have been proposed as being suitable for catalytic ammonia synthesis. Such materials include
MgO, and the like Al 2 O 3 and MgAl 2 O 4. At present, the most active ruthenium catalysts are those supported on graphitized carbon as carrier material.
【０００５】しかし、炭素に基づく支持体の使用には、
これが工業的な条件下では水素化されやすいという重大
な欠点がある。炭素系支持体はゆっくりとメタンに変化
し、そのため支持体が次第に消耗し、最後には操業が困
難となる。However, the use of carbon-based supports involves:
This has the serious disadvantage that it is susceptible to hydrogenation under industrial conditions. The carbon-based support slowly converts to methane, which gradually depletes the support and makes operation difficult in the end.
【０００６】[0006]
【発明が解決しようとする課題及び課題を解決するため
の手段】本発明の一般的な課題は、支持材料として窒化
ホウ素及び／または窒化ケイ素からなる改善されたキャ
リアを有する、ルテニウムに基づくアンモニア合成触媒
を提供することである。窒化物は炭素と等電子である。
窒化ホウ素及び窒化ケイ素は双方とも、炭素と同様に、
幾つかの同素体として存在する。これらの同素体のうち
の一つは、通常ホワイトグラファイトと呼ばれる黒鉛性
形態のものである。炭素とは異なり、窒化ホウ素及び窒
化ケイ素は、工業的なアンモニア合成条件下で熱力学的
に安定である。SUMMARY OF THE INVENTION A general object of the present invention is to provide a ruthenium-based ammonia synthesis with an improved carrier comprising boron nitride and / or silicon nitride as a support material. It is to provide a catalyst. Nitride is isoelectronic with carbon.
Both boron nitride and silicon nitride, like carbon,
There are several allotropes. One of these allotropes is in a graphitic form, commonly called white graphite. Unlike carbon, boron nitride and silicon nitride are thermodynamically stable under industrial ammonia synthesis conditions.
【０００７】BN及びSi3N4 の双方とも、高表面積の材料
(>25m2/g) として得ることができ、また当業界において
公知の方法によって適当なキャリアに成形することがで
きる。[0007] Both BN and Si 3 N 4 are high surface area materials
(> 25 m 2 / g) and can be formed into a suitable carrier by methods known in the art.
【０００８】BNまたはSi3N4 上に支持された、促進(pro
motion) されたルテニウム触媒は、接触アンモニア合成
の間、完全に安定している。A promoter (pro) supported on BN or Si 3 N 4
The motioned ruthenium catalyst is completely stable during catalytic ammonia synthesis.
【０００９】それゆえ、本発明は、アンモニア合成にお
いて、触媒活性材料としてルテニウムを有するアンモニ
ア合成触媒に、触媒キャリアとして窒化ホウ素及び／ま
たは窒化ケイ素を使用する。Therefore, the present invention uses boron nitride and / or silicon nitride as a catalyst carrier in an ammonia synthesis catalyst having ruthenium as a catalytically active material in ammonia synthesis.
【００１０】BN及びSi3N4 は、商業的な製品として入手
することもできるし、または業界公知の方法によって製
造することができる。これらの窒化物支持体の表面積は
好ましくは25m2/gを超える。また、これらの窒化物支持
体は、アンモニアによって処理される間に窒化物に変化
するSi及びＢ前駆体からも得られる。[0010] BN and Si 3 N 4 can be obtained as commercial products or can be made by methods known in the art. The surface area of these nitride supports is preferably greater than 25 m 2 / g. These nitride supports are also obtained from Si and B precursors that change to nitride while being treated with ammonia.
【００１１】ルテニウムは、慣用の方法、例えば適当な
含ルテニウム化合物、例えば塩化物または酢酸塩を用い
て含浸処理することによって支持体に導入する。The ruthenium is introduced into the support in a conventional manner, for example by impregnation with a suitable ruthenium-containing compound, for example a chloride or acetate.
【００１２】促進処理の前に、触媒を、還元性ガス、例
えば水素または合成ガスで処理することによって還元す
ることができる。[0012] Prior to the accelerated treatment, the catalyst can be reduced by treating it with a reducing gas, such as hydrogen or synthesis gas.
【００１３】促進処理は、促進剤の塩を含浸させること
によって行うことができる。促進剤は、公知のアンモニ
ア合成触媒用促進剤、すなわちアルカリまたはアルカリ
土類金属からあるいは希土類金属から選択される。The accelerating treatment can be carried out by impregnating a salt of an accelerating agent. The promoter is selected from the known promoters for ammonia synthesis catalysts, ie alkali or alkaline earth metals or rare earth metals.
【００１４】各促進剤は、順次または一緒に導入するこ
とができる。The accelerators can be introduced sequentially or together.
【００１５】[0015]
【実施例】例１ 触媒の調製 窒化ホウ素支持体（六方晶系、表面積85m2/g、粉末Ｘ線
回折で測定した結晶サイズ 7.5nm）を、ニトロソ硝酸ル
テニウムで含浸処理し、５重量％のRu濃度を得る。この
含浸処理したサンプルを80℃で乾燥しそして450 ℃で二
水素(dihydrogen)の流れ中で還元する。このサンプルに
“5RuBN ”と標付けする。EXAMPLE 1 Preparation of Catalyst A boron nitride support (hexagonal, surface area 85 m 2 / g, crystal size 7.5 nm as measured by powder X-ray diffraction) was impregnated with ruthenium nitroso nitrate and 5% by weight. Obtain Ru concentration. The impregnated sample is dried at 80 ° C. and reduced at 450 ° C. in a stream of dihydrogen. Label this sample "5RuBN".
【００１６】７重量％のRuを含む他のサンプルを同様に
して作製する。このサンプルには“7RuBN ”と標付けす
る。その触媒密度は約1.5 ｇ/ml である。 例２ セシウムによる触媒の促進 5RuBN 及び7RuBN を硝酸セシウムの水溶液で含浸処理
し、３重量％のセシウム濃度を得る。これらのサンプル
にそれぞれ3Cs5RuBN及び3Cs7RuBNと標付けする。 例３ バリウムによる触媒の促進 5RuBN 及び7RuBN を硝酸バリウムの水溶液で含浸処理
し、３重量％のバリウム濃度を得る。これらのサンプル
にそれぞれ3Ba5RuBN及び3Ba7RuBNと標付けする。 例４ 触媒の試験 上記触媒を、100bar及び400 ℃で運転した恒温プラグ流
れ(plug flow) 反応器中で試験する。入口ガスは、二水
素／二窒素の3:1 混合物中に4.5 ％のアンモニアを含
む。その流れは、出口において12％のアンモニアを得る
ために調節する。これらの条件下に、上記触媒は、一時
間、触媒１ｇ当たり生産されるアンモニアのmlとして表
される異なる率でアンモニアを生産する。 触媒 ml NH3/(g4h) 5RuBN 140 7RuBN 190 3Cs5RuBN 1150 3Cs7RuBN 1320 3Ba5RuBN 4600 3Ba7RuBN 4930 例５ 触媒の熱安定性 触媒の安定性を評価するために、3Ba5RuBN及び3Ba7RuBN
を上記反応器中550 ℃で1000時間加熱する。これらの条
件下に、アンモニアの出口濃度は約7.0 ％である。この
処理の後、これらの触媒を再び試験する。 触媒 ml NH3/(g4h) 3Ba5RuBN 4580 3Ba7RuBN 4960 例６ 触媒の失活及び再活性化 失活後に触媒を再活性化できるかどうかを調べるため
に、例５の触媒（3Ba5RuBN) を、N2中で10時間、1000pp
m のO2で室温で処理し、次いで周囲雰囲気に曝した。次
に、これを再び反応器に入れ、そして同じ条件下に試験
した。 触媒 ml NH3/(g4h) 3Ba5RuBN 4610Another sample containing 7% by weight of Ru is prepared in a similar manner. This sample is labeled “7RuBN”. Its catalyst density is about 1.5 g / ml. Example 2 Catalyst promotion by cesium 5RuBN and 7RuBN are impregnated with an aqueous solution of cesium nitrate to obtain a cesium concentration of 3% by weight. These samples are labeled 3Cs5RuBN and 3Cs7RuBN, respectively. Example 3 Promoting the catalyst with barium 5RuBN and 7RuBN are impregnated with an aqueous solution of barium nitrate to obtain a barium concentration of 3% by weight. These samples are labeled 3Ba5RuBN and 3Ba7RuBN, respectively. Example 4 Catalyst Testing The above catalyst is tested in a constant temperature plug flow reactor operating at 100 bar and 400 ° C. The inlet gas contained 4.5% ammonia in a 3: 1 mixture of dihydrogen / dinitrogen. The flow is adjusted to obtain 12% ammonia at the outlet. Under these conditions, the catalyst produces ammonia at different rates, expressed as ml of ammonia produced per gram of catalyst for one hour. Catalyst ml NH 3 / (g 4 h) 5RuBN 140 7RuBN 190 3Cs5RuBN 1150 3Cs7RuBN 1320 3Ba5RuBN 4600 3Ba7RuBN 4930Example 5 Thermal stability of catalyst
Is heated at 550 ° C. for 1000 hours in the above reactor. Under these conditions, the outlet concentration of ammonia is about 7.0%. After this treatment, the catalysts are tested again. Catalyst ml NH 3 / (g 4 h) 3Ba5RuBN 4580 3Ba7RuBN 4960 Example 6 Deactivation and Reactivation of Catalyst To determine whether the catalyst can be reactivated after deactivation, the catalyst of Example 5 (3Ba5RuBN) was converted to N 2 hours for 10 hours, 1000pp
m 2 O 2 at room temperature and then exposed to the ambient atmosphere. It was then put back into the reactor and tested under the same conditions. Catalyst ml NH 3 / (g 4 h) 3Ba5RuBN 4610
Claims (2)
ャリアに支持された、触媒活性材料としてのルテニウム
を含んでなる触媒を、アンモニア生成条件下にアンモニ
ア合成ガスと接触させることによって、アンモニア合成
ガスからアンモニアを製造する方法。1. A method comprising the steps of: contacting a catalyst comprising ruthenium as a catalytically active material, supported on a carrier of boron nitride and / or silicon nitride, with an ammonia synthesis gas under conditions for producing ammonia, from the ammonia synthesis gas. A method for producing ammonia.
支持されたルテニウムを含んでなる、アンモニア合成ガ
スからのアンモニアの合成に活性を示す触媒。2. A catalyst active in the synthesis of ammonia from an ammonia synthesis gas, comprising ruthenium supported on boron nitride and / or silicon nitride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16215199P | 1999-10-29 | 1999-10-29 | |
| US60/162151 | 1999-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001149780A true JP2001149780A (en) | 2001-06-05 |
Family
ID=22584376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000328905A Withdrawn JP2001149780A (en) | 1999-10-29 | 2000-10-27 | Method for manufacturing ammonia and ammonia synthesizing gas |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US6479027B1 (en) |
| EP (1) | EP1095906B1 (en) |
| JP (1) | JP2001149780A (en) |
| KR (1) | KR20010051302A (en) |
| CN (1) | CN1170770C (en) |
| AT (1) | ATE285992T1 (en) |
| AU (1) | AU779326B2 (en) |
| CA (1) | CA2324328C (en) |
| DE (1) | DE60017055T2 (en) |
| MX (1) | MXPA00010606A (en) |
| RU (1) | RU2247600C2 (en) |
| TW (1) | TWI225035B (en) |
| ZA (1) | ZA200006022B (en) |
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| JP3672367B2 (en) | 1995-12-20 | 2005-07-20 | 三井化学株式会社 | Ammonia synthesis catalyst and production method thereof |
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- 2000-10-16 DE DE60017055T patent/DE60017055T2/en not_active Expired - Fee Related
- 2000-10-16 EP EP00122537A patent/EP1095906B1/en not_active Expired - Lifetime
- 2000-10-16 AT AT00122537T patent/ATE285992T1/en not_active IP Right Cessation
- 2000-10-18 TW TW089121752A patent/TWI225035B/en not_active IP Right Cessation
- 2000-10-20 US US09/692,037 patent/US6479027B1/en not_active Expired - Fee Related
- 2000-10-26 CA CA2324328A patent/CA2324328C/en not_active Expired - Lifetime
- 2000-10-26 ZA ZA200006022A patent/ZA200006022B/en unknown
- 2000-10-27 MX MXPA00010606A patent/MXPA00010606A/en active IP Right Grant
- 2000-10-27 RU RU2000126938/04A patent/RU2247600C2/en active
- 2000-10-27 JP JP2000328905A patent/JP2001149780A/en not_active Withdrawn
- 2000-10-27 AU AU69599/00A patent/AU779326B2/en not_active Expired
- 2000-10-28 KR KR1020000063683A patent/KR20010051302A/en not_active Application Discontinuation
- 2000-10-28 CN CNB001344188A patent/CN1170770C/en not_active Expired - Lifetime
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2002
- 2002-09-17 US US10/244,677 patent/US6764668B2/en not_active Expired - Lifetime
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| JP2018528849A (en) * | 2015-07-09 | 2018-10-04 | ユミコア アクチェンゲゼルシャフト ウント コンパニー コマンディートゲゼルシャフト | Three-way catalyst with NH3-SCR activity, ammonia oxidation activity and adsorption capacity for volatile vanadium and tungsten compounds |
| WO2018030394A1 (en) * | 2016-08-08 | 2018-02-15 | 国立大学法人東京工業大学 | Method for manufacturing ammonia synthesis catalyst, and method for manufacturing ammonia |
| JPWO2018030394A1 (en) * | 2016-08-08 | 2019-04-18 | 国立大学法人東京工業大学 | Method for producing catalyst for ammonia synthesis and method for producing ammonia |
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| US11964260B2 (en) | 2016-08-08 | 2024-04-23 | Tokyo Institute Of Technology | Method for manufacturing ammonia synthesis catalyst, and method for manufacturing ammonia |
| WO2019156028A1 (en) * | 2018-02-07 | 2019-08-15 | 国立大学法人東京工業大学 | Composite, method for manufacturing composite, catalyst, and method for manufacturing ammonia |
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| JPWO2019156029A1 (en) * | 2018-02-07 | 2021-01-28 | 国立大学法人東京工業大学 | Method for producing composites, catalysts and ammonia |
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| JP7427797B2 (en) | 2020-05-07 | 2024-02-05 | コリア・インスティテュート・オブ・サイエンス・アンド・テクノロジー | A catalyst in which a catalytic metal is supported on a support with a hexagonal crystal structure, and a method for producing the same |
| KR20220131726A (en) * | 2021-03-22 | 2022-09-29 | 원형일 | A nitride catalysts for synthesize ammonia at low temperature and low temperature ammonia synthesis from water and air by using nitride catalysts |
| KR102594504B1 (en) | 2021-03-22 | 2023-10-26 | 원형일 | A nitride catalysts for synthesize ammonia at low temperature and low temperature ammonia synthesis from water and air by using nitride catalysts |
Also Published As
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| RU2247600C2 (en) | 2005-03-10 |
| ZA200006022B (en) | 2001-08-24 |
| AU6959900A (en) | 2001-05-03 |
| US6479027B1 (en) | 2002-11-12 |
| DE60017055D1 (en) | 2005-02-03 |
| US20030017097A1 (en) | 2003-01-23 |
| CN1294089A (en) | 2001-05-09 |
| US6764668B2 (en) | 2004-07-20 |
| EP1095906A3 (en) | 2002-03-20 |
| EP1095906A2 (en) | 2001-05-02 |
| EP1095906B1 (en) | 2004-12-29 |
| CN1170770C (en) | 2004-10-13 |
| DE60017055T2 (en) | 2005-05-25 |
| CA2324328A1 (en) | 2001-04-29 |
| KR20010051302A (en) | 2001-06-25 |
| TWI225035B (en) | 2004-12-11 |
| CA2324328C (en) | 2011-01-25 |
| MXPA00010606A (en) | 2002-07-09 |
| AU779326B2 (en) | 2005-01-20 |
| ATE285992T1 (en) | 2005-01-15 |
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